Cleaning and softening detergent compositions

ABSTRACT

Detergent compositions containing a synthetic organic nonsoap detergent and an organo-phosphorus softener compound which provide conjoint cleaning and softening properties are described. The organo-phosphorus compounds employed in an amount of about 1 to 15 percent of the composition include alkylphosphinic compounds having the formula WHEREIN R is alkyl of about 12 to 30 carbon atoms, R1 is hydrogen or alkyl of one to about 30 carbon atoms, and M is a water-solubilizing cation, e.g., hydrogen, alkali metal, ammonium or substituted-ammonium or alkyl of about one to about eight carbon atoms; and alkyldiphosphonic compounds having the formula

United States Patent [72] inventor Melvin A. Barber:

Mt. Healthy, Ohio [21] Appl. No. 739,631 [22] Filed June 25, 1968 [45] Patented Sept. 28, 1971 [73] Assignee The Procter 8r Gamble Company Cincinnati, Ohio [54] CLEANING AND SOFIENING DETERGENT COMPOSITIONS 11 Claims, No Drawings [52] U.S. Cl 252/8.6, 117/l39.5, 252/8.75, 252/8.8, 252/89, 252/137, 252/138, 252/161 [51] Int.Cl D06m 13/28,.

Cl 1d 3/065 [50] Field of Search 252/8.8, 86,135, 8.75, 137,138, 161; 117/1395 O [56] References Cited UNITED STATES PATENTS 2,286,794 6/1942 Dickey et a1 252/8.8 2,594,454 4/1952 Kosolapoff..... 260/973 2,929,788 3/1960 Freese et al..... 252/137 3,299,123 1/1967 Fitch et a1 260/932 3,313,735 4/1967 McCune 252/152 3,360,470 12/1967 Wixon.. 252/137 3,450,637 6/1969 Drew 252/137 3,454,494 7/1969 Clark et a1. 252/8.8

FOREIGN PATENTS 915,984 8/1954 Germany Primary Examinerl-lerbert B. Guynn Attrneys-Richard C. Witte, Julius P. Filcik and Louis G.

Xiarhos ABSTRACT: Detergent compositions containing a synthetic organic nonsoap detergent and an organo-phosphorus softener compound which provide conjoint cleaning and softening properties are described. The organo-phosphorus compounds employed in an amount of about 1 to percent of the composition include alkylphosphinic compounds having the formula l oM wherein R is alkyl of about 12 to carbon atoms, R is hydrogen or alkyl of one to about 30 carbon atoms, and M is a water-solubilizing cation, e.g., hydrogen, alkali metal, ammonium or substituted-ammonium or alkyl of about one to about eight carbon atoms; and alkyldiphosphonic compounds having the formula wherein R is alkyl of about 12 to about 30 carbon atoms and each M is a water-solubilizing cation, e.g., hydrogen, alkali metal, ammonium, substituted ammonium or alkyl of 1 to about 8 carbon atoms. Also disclosed is a process ofconjointly washing and softening textile materials which comprises washing textiles at a temperature of about to about F.

, with an aqueous solution of a detergent composition of the present invention, said solution having at least about 16 ppm of the organo-phosphorus softener compound.

CLEANING AND SOFIENING DETERGENT COMPOSlTlONS BACKGROUND OF THE. INVENTION This invention relates to detergent compositions. More particularly, it relates to detergent compositions exhibiting superior softening as well as cleaning properties.

The use of synthetic detergent compositions in heavy-duty laundering is a widespread practice. The compositions conventionally employed generally comprise a synthetic detergent and an alkaline builder material which functions to enhance the cleaning level of the detergent compound. Such detergent formulations have been known to have a tendency to react with the metal ions present in the washing solution precipitating out insoluble salts which deposit on the textile material being laundered. These deposited mineral salts weaken the laundered fabric, particularly at those areas of the fabric which are exposed to frictional and creasing effects such as collars and cuffs. This weakening of laundered fabrics and resulting loss of useful life which is encountered in the course of frequent laundering have in part resulted in the need for softener formulations capable of improving the softness or hand" of laundered textiles. It has been found that the treatment of such textiles with softening agents improves their softness or feel and prolongs their useful life. In addition, it has been found that such a treatment generally results in a reduced tendency of the treated fabric to accumulate electrical charges which facilitates the ironing of such fabric.

The compositions most commonly employed in home laundering processes for the treatment of fabrics to improve softness or "hand normally are liquid fabric softener compositions which contain a quaternary ammonium active component in a water vehicle. These quaternary compounds have an affinity for negatively charged fibers and normally have at least one long-chain alkyl group of from 16 to about 20 carbon atoms.

Inasmuch as quaternary ammonium compounds are often incompatible with certain detergent compounds, particularly anionic detergent compounds, and interact to form complexes which exhibit neither the desired washing nor softening properties, the use of such materials together in the same formulation has been largely avoided. This incompatibility problem has been obviated in part by employing quaternary ammonium-containing softener formulations in the final rinse of the laundering process, i.e., at a time subsequent to the washing step.

OBJECTS OFTHEJ VENL QN It is an object of the present invention to provide composi-. tions useful for laundering textile materials to provide conjointly superior levels of cleaning and softening.

It is a further object of the present invention to provide. laundering compositions containing an organic detergent and a softener component compatible therewith.

It is another object of the present invention to provide a process of laundering textile materials whereby the laundered materials are subjected to the conjoint action of cleaning and softening.

Other objects of the present invention will become apparent from the description of the invention which hereinafter follows.

MARY QEIHE,.I 1Y EL I .QN These and other objects were achieved in accordance with the present invention which comprises detergent compositions consisting essentially of l a synthetic organic nonsoap detergent; and (2 about I percent to about l5 percent of a compatible organic phosphorus-containing softener compound selected from the group consisting of a. alkylphosphinic compounds having the formula wherein R is alkyl of about 12 to 30 carbon atoms, R is hydrogen or alkyl ofone to about 39 carbon atornsand M is a water-solubilizing cation, e.g., hydrogen, alkali metal, ammonium or substitutedammonium or alkyl of about one to about eight carbon atoms; and

b. alkyldiphosphonic compounds having the formula wherein R is alkyl of about 12 to about 30 carbon atoms and leach M is a water-solubilizing cation, e.g., hydrogen, alkali metal, ammonium, substituted ammonium or alkyl of one to about eight carbon atoms.

Also provided by the present invention is a process of con- |jointly washing and softening textile materials which comprises washing textile materials at a temperature of about 40 to about F with an aqueous solution of a detergent composition hereinbefore described, the solution containing at least about 16 p.p.m. of organic phosphorus-containing sof- E t 2 m 9- 7.. .7 .7

DETAILED DESCRIPTION OF THE lNVENTlON The organo-phosphorus softening agents of the present invention are effective in the presence of a wide variety of synthetic organic detergents. These detergents are synthetic anionic, nonionic, ampholytic and zwitterionic nonsoap detergents characterized by their high solubility in water, their resistance to precipitation by the constituents of hard water and their surface active and effective detergent properties.

Synthetic nonsoap detergents utilizable herein include:

1. Anionic synthetic detergents: This class of synthetic detergents can be broadly described as the water-soluble salts, particularly the alkali metal (sodium, potassium, etc.) salts, or organic sulfuric reaction products having in the molecular structure an alkyl radical containing from about eight to about 22 carbon atoms and a radical selected from the group con sisting of sulfonic acid and sulfuric acid ester radicals. important examples of the synthetic detergents which form a part of the preferred compositions of the present invention are the sodium or potassium alkyl sulfates, especially those obtained by sulfating the higher alcohols produced by reducing the glycerides of tallow or coconut oil; sodium or potassium alkyl benzene sulfonates, in which the alkyl group in a straight or branched chain contains from about nine to about 18 carbon atoms, especially those of the types described in U.S. Pat. Nos. 2,220,099 and 2,477,383; sodium alkyl glyceryl ether sulfonates, especially those ethers of the higher alcohols derived from tallow and coconut oil; sodium salts of sulfonated a olefms containing eight to 22 carbon atoms, e.g., those described in U.S. Pat. No. 3,332,880, issued July 25, 1967 to Kessler et aL, sodium coconut oil fatty acid monoglyceride sulfates and sulfonates; sodium or potassium salts of sulfuric acid esters of the reaction product of one mole of a higher fatty alcohol (e.g., tallow or coconut oil alcohols) and about three moles of ethylene oxide; sodium or potassium salts of alkyl phenol ethylene oxide ether sulfate with about four units of ethylene oxide per molecule and in which the alkyl radicals contain about nine carbon atoms; the reaction product of fatty acids esterified with isethionic acid and neutralized with sodium hydroxide where, for example, the fatty acids are derived from coconut oil; sodium or potassium salts of fatty acid amide of a methyl taurine in which the fatty acids, for example, are derived from coconut oil; and others known in the art. a number being specifically set forth in U.S. Pat. Nos. 2,486,92 l, 2,486,922 and 2,396,278

2. Nonionic synthetic detergents: This class of synthetic detergents may be broadly defined as compounds produced by the condensation of alkylene oxide groups (hydrophilic in nature) with an organic hydrophobic compound, which may be aliphatic or alkyl aromatic in nature. The length of the hydrophilic or polyoxyalkylene radical which is condensed with any particular hydrophobic group can be readily adjusted to yield a waterhsoluble compound having the desired degree of balance between hydrophilic and hydrophobic elements.

For example, a well-known class of nonionic synthetic detergents is made available on the market under the trade name of Pluronic." These compounds are formed by condensing ethylene oxide with a hydrophobic base formed by the condensation of propylene oxide with propylene glycol. The hydrophobic portion of the molecule which, of course, exhibits water insolubility has a molecular weight of from about 1,500 to 1,800 The addition of polyoxyethylene radicals to this hydrophobic portion tends to increase the water solubility of the molecule as a whole and the liquid character of the products is retained up to the point where the polyoxyethylene content is about 50 percent of the total weight of the condensation product.

Other suitable nonionic synthetic detergents include:

i. The polyethylene oxide condensates of alkyl phenols, e.g.,

the condensation products of alkyl phenols having an alkyl group containing from about six to 12 carbon atoms in either a straight chain or branched chain configuration, with ethylene oxide, the said ethylene oxide being present in amounts equal to 10 to 25 moles of ethylene oxide per mole of alkyl phenol. The alkyl substituent in such compounds may be derived from polymerized propylene, diisobutylene, octane, or nonane, for example. Those derived from the condensation of ethylene oxide with the product resulting from the reaction of propylene oxide and ethylene diamine-products which may be varied in composition depending upon the balance between the hydrophobic and hydrophilic elements which is desired. For example, compounds containing from about 20 percent to about 80 percent polyoxyethylene by weight and having a molecular weight of from about 5,000 to about li,000 resulting from the reaction of ethylene oxide groups with a hydrophobic base constituted of the reaction product of ethylene diamine and excess propylene oxide, said base having a molecular weight on the order of 2,500 to 3,000 are satisfactory.

iii. The condensation product of aliphatic alcohols having from eight to 18 carbon atoms, in either straight chain or branched chain configuration, with ethylene oxide, e.g., a coconut alcohol ethylene oxide condensate having from 10 to 30 moles of ethylene oxide per mole of coconut alecho], the coconut alcohol fraction having from 10 to 14 carbon atoms.

3. Long chain tertiary amines oxides (nonionic detergents) corresponding to the following general formula, R, R, R, N 0, wherein R, contains an alkyl alkenyl or monohydroxy alkyl radical of from about eight to about 18 carbon atoms from zero to about l ethylene oxide moieties, and from zero to one glyceryl moiety, and R, and R contain from one to about .three carbon atoms and from zero to about one hydroxy group, e.g., methyl, ethyl, propyl, hydroxy ethyl, or hydroxy propyl radicals. The arrow in the formula is a conventional representation of a semipolar bond. Examples of amine oxides suitable for use in this invention include dimethyldodecyl amine oxide, oleyldi(2 -hydroxyethyl) amine oxide, dimethyloctylarnine oxide, dimethyldecylamine oxide, dimethyltetradecylamine oxide, 3, 6, 9 trioxaheptadecyldiethylamine oxide, di(2 -hydroxyethyl) tetradecylamine oxide, 2 -dodecoxy ethyl dimethylamine oxide, 3 -dodecoxy-2 hydroxy propyl di(3 -hydroxypropyl) -amine oxide, dimethylhexadecylamine oxide.

4. Long chain tertiary phosphine oxides (nonionic detergents) corresponding to the following general formula RR'R"P-- 0 wherein R contains an alkyl, alkenyl or monohydroxyalkyl radical ranging from eight to 18 carbon atoms in chain length from zero to about 10 ethylene oxide moieties and from zero to one glyceryl moiety and R and R" are each alkyl or monohydroxyalkyl groups containing from one to three carbon atoms. The arrow in the formula is a conventional representation of a semipolar bond. Examples of suitable phosphine oxides are:

dodecyldimethylphosphine oxide,

tetradecyldimethylphosphine oxide,

tetradecylmethylethylphosphine oxide,

3, 6, 9-trioxaoctadecyldimethylphosphine oxide,

cetyldimethylphosphine oxide,

3-dodecoxy-2-hydroxypropyldi (Z-hydroxyethyl) phosphine oxide,

stearyldimethylphosphine oxide,

cetylethylpropylphosphine oxide,

oleyl diethylphosphine oxide,

dodecyldiethylphosphine oxide,

tetradecyldiethylphosphine oxide,

dodecyldipropylphosphine oxide,

dodecyldi(hydroxymethyl) phosphine oxide,

dodecyldi( 2-hydroxyethyl) phosphine oxide,

tetradecylmethyl-2-hydroxypropyl phosphine oxide,

oleydimethylphosphine oxide, and

2-hydroxydodecyldimethylphosphine oxide. 5 Long chain dialkyl sulfoxides containing one short chain alkyl or hydroxy alkyl radical of one to about three carbon atoms (usually methyl) and one long hydrophobic chain which contains alkyl, alkenyl, hydroxy alkyl, or keto alkyl radicals containing from about eight to about 20 carbon atoms, from zero to about 10 ethylene oxide moieties and from zero to one glyceryl moiety. Examples include:

octadecyl methyl sulfoxide, Z-ketotridecyl methyl sulfoxide 3, 6, 9-trioxaoctadecyl Z-hydroxyethyl sulfoxide dodecyl methyl sulfoxide oleyl 3-hydroxy propyl sulfoxide tetradecyl methyl sulfoxide 3-methoxytridecyl methyl sulfoxide S-hydroxytridecyl methyl sulfoxide 3-hydroxy-4-dodecoxybutyl methyl sulfoxide 6. Ampholytic synthetic detergents can be broadly described as derivatives of aliphatic secondary and tertiary amines in which the aliphatic radical can be straight chain or branched and wherein one of the aliphatic substituents contains from about eight to about 18 carbon atoms and one contains an anionic water solubilizing group, e.g., carboxy, sulfonate, sulfate, phosphate, or phosphonate. Examples of compounds falling within this definition are sodium 3- dodecylaminopropionate, sodium 3-dodecylaminopropane sulfonate, dodecyl-beta-alanine, N-aikyl-taurines such as the one prepared by reacting dodecylamine with sodium isethionate according to the teaching of [1.8. Pat. No. 2,658,072, N-higher alkyl aspartic acids such as those produced according to the teaching of US. Pat. No. 2,438,09l, and the products sold under the trade name Miranol" and described in U.S. Pat. No. 3,528,378.

7. Zwitterionic synthetic detergents can be broadly described as derivatives of aliphatic quaternary ammonium, phosphonium, and sulfonium compounds, in which the aliphatic radicals can be straight chain or branched, and wherein one of the aliphatic substituents contains from about eight to 18 carbon atoms and one contains an anionic water solubilizing group, e.g., carboxy, sulfonate, sulfate, phosphate, or phosphonate. A general formula for these compounds is:

wherein R contains an alkyl, alkenyl, or hydroxy alkyl radical of from about eight to about 18 carbon atoms, from zero to 10 ethylene oxide moieties and from zero to one glyceryl moiety; Y is selected from the group consisting of nitrogen. phosphorous, and sulfur atoms; R is an alkyl or monohydroxy alkyl group containing one to about three carbon atoms A: is 1 when l is a sulfur atom and 2 when l is a nitrogen or phosphorous atom, R is an alkylene or hydroxy alkylene of from one to about four carbon atoms and Z is a radical selected from the group consisting of carboxylate, sulfonate,

sulfate, phosphonate, and phosphate groups. Other examples include:

4[N,N-di(2-hydroxyethyl)-N-octadecylammonio]-butanelcarboxylate; 5-[S-3hydroxypropyl-S-hexadecylsulfonio]-3-hydroxypentane-l-sulfate;

3 P,P-diethyl-P-3, 6, 9-trioxatetracosanephosphonio1-2- hydroxypropane- 1 phosphate;

3-[N,N-dipropyl-N-3-dodecoxy-2-hydroxypropylammonio]propane-l-phosphonate;

3-( N ,N-dimethyl-N-hexadecylammonio )propanel -sulfonate, 3(N,N-dimethyl-N-hexadecylarnmonio)-2- hydroxypropane-lsulfonate, 4[N-N-di(2-hydroxyethyl)- N-( 2-hydroxydodecyl)ammonio1-butanel -carboxylate, 3-[S-ethyl S-(3-dodecoxy-2hydroxypropyl)sulfonio]- propane- 1 -phosphate, 3 P,P-dimethyl-P- dodecylphosphonio]-propane-l-phosphonate, and S- [N ,N-di( 3-hydroxypropyl )-N-hexadecylammonio 2- hydroxypentane-l-sulfate. 3Examples of compounds falling within this definition are 3 -(N,N-dimethyl-N-hexadecylarnmonio)propane-l-sulfonate and 3-(N,N- dimethyl-N-hexadecylam monio )-2-hydroxy propanel sulfonate which are especially preferred for their excellent cool water detergency characteristics.

The alkyl groups contained in said detergents can be straight or branched, preferably straight, and saturated or unsaturated as desired. The above list of detergents is exemplary and not limiting. Mixtures of the above detergents can be used.

Particularly preferred organic detergents include alkali metal (sodium, potassium, lithium) alkyl benzene sulfonates, alkali metal alkyl sulfates, and mixtures thereof wherein the alkyl group is of straight or branched chain configuration and contains about nine to about 18 carbon atoms. Specific compounds preferred from the standpoints of superior performance characteristics and ready availability include the following: sodium decyl benzene sulfonate, sodium dodecyl benzene sulfonate, sodium tridecyl benzene sulfonate, sodium tetradecyl benzene sulfonate, sodium hexadecyl benzene sulfonate, sodium octadecyl sulfate, sodium hexadecyl sulfate and sodium tetradecyl sulfate.

The detergent compositions of the present invention can contain water-soluble, builder salts either of the organic or inorganic type. Thus, the softening effects of the organic phosphorus-containing softener compounds of the present invention can be embodied in both built and unbuilt detergent compositions. Since built detergent formulations are preferred from the standpoint of enhanced cleaning, preferred compositions herein are those containing builders of the hereinbeforedescribed type. These builder materials are employed in the compositions of the present invention in ratio by weight of builder to organic detergent of about 30:1 to 0.25:1. Preferably, a ratio of builder to detergent of about 9:1 to about 0.521 is employed.

Examples of suitable water-soluble, inorganic alkaline detergency builder salts are alkali metal carbonates, borates, phosphates, polyphosphates, bicarbonates, silicates and sulfates. Specific examples of such salts are sodium and potassium tetraborates, bicarbonates, carbonates, tripolyphosphates, pyrophosphates, orthophosphates and hexametaphosphates.

Examples of suitable organic alkaline detergency builder salts are: l) Water-soluble aminopolycarboxylates, e.g., sodium and potassium ethylenediaminetetraacetates, nitrilotriacetates and N-(Z-hydroxyethyl) -nitrilo diacetates; (2) Watersoluble salts of phytic acid, e.g., sodium 3) potassium phytatessee U.S. Pat, No. 2,739,942; (3) Water-soluble, polyphosphonates, including specifically, sodium, potassium and lithium salts of ethane-Lhydroxy-l, ldiphosphonic acid, sodium potassium and lithium salts of methylene diphosphonic acid, sodium, potassium and lithium salts. of ethylene diphosphonic acid, and sodium, potassium and lithium salts of ethane-l, 1, Z-triphosphonic acid. Other examples include the alkali metal salts of ethane-Z-carboxy-l, ldiphosphonic acid, hydroxymethanediphosphonic acid, carbonyldiphosphonic acid, ethane-l-hydroxy -l, l, 2- triphosphonic acid, ethene-2-hydroxy-l, l, 2-triphosphonic acid, propane-1, l, 3, 3- tetraphosphonic acid, propane-l, l, 2, 3-tetraphosphonic acid, and propane-l, 2, 2, 3- tetraphosphonic acid; (3) Water-soluble salts of polycarboxylate polymers and copolymers as described in the patent of Francis L. Diehl, U.S. Pat. No. 3,308,067, issued Mar. 7, 1967. Specifically, a detergent builder material comprising a water-soluble salt of a polymeric aliphatic polycarboxylic acid having the following structural relationships as to the position of the carboxylate groups and possessing the following prescribed physical characteristics: (a) a minimum molecular weight of about 350 calculated as to the acid form; (b) an equivalent weight of about 50 to about calculated as to acid form; (c) at least 45 mole percent of the monomeric species having at least two carboxyl radicals separated from each other by not more than two carbon atoms; (d) the site of attachment to the polymer chain of any carboxyl-containing radical being separated by not more than three carbon atoms along the polymer chain from the site of attachment of the next carboxyl-containing radical. Specific examples are polymers of itaconic acid, aconitic acid, maleic acid, mesaconic acid, fumaric acid, methylene malonic acid, and citraconic acid and copolymers with themselves and other compatible monomers such as ethylene; and (5) mixtures thereof.

Mixtures of organic and/or inorganic builders can be used and are generally desirable. One such mixture of builders is disclosed in Canadian Pat. No. 755,038 of Burton H. Gedge, e.g., ternary mixtures of sodium tripolyphosphate, sodium nitrilotriacetate and trisodium ethane-l-hydroxy-l, l diphosphonate. The above-described builders can also be utilized singly in this invention. Especially preferred builders that can be used singly or in combination in this invention include tetra sodium pyrophosphate and sodium tripolyphosphate.

The fabric-substantive organic phosphorus-containing softener compounds employed in detergent compositions according to the present invention impart improved hand or feel to the laundered fabrics. As there will be considerable variation in the strengths of washing solutions employed by different users, i.e., some users may tend to use more or less than others, the requisite amount of softener compound employed in the detergent compositions of the present invention is an amount sufficient to impart improved hand or feel to the laundered fabric. Normally, the fabric-substantive softener compounds of the present invention are employed in a range of about 1 percent to about 15 percent by weight of the detergent composition to provide about 16 to about 240 ppm. of softener compound in washing solution. A preferred range of softener compound is about 2 percent to about 7 percent and is preferred from the standpoints of superior softening effects and economy; it provides about 32 to about 112 p.p.m. in washing solution.

The phosphinate softener compounds utilizable herein to impart lubricity and improved feel or hand to laundered textiles have the formula wherein R is alkyl of about 12 to about 30 carbon atoms, R is hydrogen or alkyl of one to about 30 carbon atoms, and M is a water-solubilizing cation or alkyl as defined hereinbefore.

These compounds can be characterized generally as having one or two P-C linkages in their molecules and are described herein by the general terms phosphinic acids, salts of phosphinic acids and esters of phosphinic acids. As employed herein, the general term phosphinate compound is intended as embracing the acid, salt and ester forms described herein.

The phosphinate compounds of the present invention are characterized by the presence of at least one long chain alkyl group of at least 12 carbon atoms which serves to provide improved softness or hand to treated textile materials. This alkyl, which corresponds to R in the hereinbefore described formula, can be either branched or unbranched and can be primary, secondary or tertiary. The phosphinate compounds of the present invention can also contain an additional P-C linkage in the form of an alkyl of up to about 30 carbon atoms which can also be branched, unbranched, primary, secondary or tertiary.

Preferred phosphinate compounds are dialkylphosphinates characterized by the presence of two identical alkyl groups of about 16 to 24 carbon atoms. They are preferred inasmuch as they impart excellent softening properties to laundered textiles, are remarkably compatible with anionic surfactants and are readily prepared by conventional means. These dialkylphosphinate compounds are preferably employed in their acid and alkali metal forms.

The phosphinate compounds utilized herein in their salt or ester forms are those corresponding to the hereinbefore described formula wherein M is a water-solubilizing cation or alkyl of one to about eight atoms. Water-solubilizing cations include alkali metal cations (e.g., sodium, potassium, lithium), ammonium ions and substituted ammonium cations (e.g., methyldimethyl-, trimethyland tetramethylammonium, dimethyl piperdinium). Suitable alkyl M groups include methyl, ethyl, n-propyl, iso-propyl, n-buty], npentyl, n-hexyl, n-heptyl, 2-ethylhexyl, and the like, alkyl groups ofone to four carbon atoms being preferred. Alkali metal cations are preferred from the standpoints of excellent results and ready availability.

The following compounds are illustrative of the phosphinate compounds of the present invention. It will be appreciated that these are merely illustrative and not be regarded as limitative: n-dodecylphosphinic acid; n-tridecylphosphinic acid; ntetradecylphosphinic acid; n-pentadecylphosphinic acid; nhexadecylphosphinic acid; n-heptadecylphosphinic acid; n-octadecylphosphinic acid; n-nonadecylphosphinic acid; neicosylphosphinic acid; n-heneicosylphosphinic acid; ndocosylphosphinic acid; n-tricosylphosphinic acid; n-

tetracosylphosphinic acid; n-pentacosylphosphinic acid; nhexacosylphosphinic acid; n-heptacosylphosphinic acid; n-octacosylphosphinic acid; n-nonascosylphosphinic acid; ntriacontylphosphinic acid; sodium dodecylphosphinate; potassium n-tetradecyiphosphinate; lithium n-hexadecylphosphinate; sodium octadecylphosphinate; potassium n-eicosylphosphinate; sodium n-docosylphosphinate; potassium ntetracosylphosphinate; sodium n-hexacosylphosphinate; lithium n-octacosylphosphinate; lithium n-triacontylphosphinate; methyl n-dodecylphosphinate; ethyl n-tetradecylphosphinate; isopropyl n-tetradecylphosphinate; 2-ethylhexyl n-hexadecylphosphinate; methyl n-eicosylphosphinate; ethyl ntetracosylphosphinate; butyl n-octacosylphosphinate; butyl ntriacontylphosphinate; ammonium n-hexadecylphosphinate; ammonium n-octadecylphosphinate; dimethylammonium neicosylphosphinate; trimethylammonium n-eicosylphosphinate; ammonium n-tetracosylphosphinate; n-dodecylmethylphosphinic acid; n-tridecylmethylphosphinic acid; ethyl-n-tetradecylphosphosphinic acid; ethyl-n-hexadecylphosphinic acid; methyl-n-octadecylphosphinic acid; neicosylmethylphosphinic acid; n-docosylhexylphosphinic acid; di-n-dodecylphosphinic acid; di-n-hexadecylphosphinic acid; di-n-octadecylphosphinic acid; sodium methyl-n-octacosylphosphinate; potassium di-n-dodecylphosphinate; sodium di-n-tetradecylphosphinate; potassium di-n-hexadecylphosphinate; lithium di-n-octadecylphosphinate; ammonium di-n-eicosylphosphinate; sodium di-n-eicosylphosphinate; trimethylammonium di-n-docosylphosphinate; sodium di-n-hexacosylphosphinate, sodium di-n-octacosylphosphinate; sodium di-n-triacontylphosphinate; methyl di-neicosylphosphinate; 2-ethylhexyl di-n-eicosylphosphinate; and the isomers thereof.

The class of phosphinate compounds of the present invention are known compounds and can be prepared by methods known to those skilled in the art. Generally, the phosphinate compounds of the present invention can be prepared by reacting an a -olefin or mixture of a olefins with hypophosphorous acid or a salt thereof in the presence of a free-radical catalyst, e.g., t-butyl peroxide at a temperature of about 0 to C. to provide a phosphinic acid or salt thereof. When hypophosphorous acid is employed, a phosphinic acid product is obtained. Similarly, when a salt of hypophosphorous acid is employed, the phosphinate compound is obtained in the form of the salt. Depending upon molar proportions, phosphinate compounds having one or two P-C bonds are obtained, the former resulting when an excess of the hypophosphorus acid or salt is employed, the latter when about 2 moles of a -olef1n are employed per mole of hypophosphorous acid or salt. Esters of phosphinate compounds are conveniently obtained by conventional esterification methods employing the phosphinic acid form and an alkanol or by reacting an a -olefin with an ester of hypophosphorous acid. Suitable methods of preparing phosphinate compounds of the present invention are found in U.S. Pat. No. 2,957,931 issued Oct. 25, 1960 to Hamilton et al., and in US, Pat. No. 3,092,650 issued June 4, 1963, to McBride, Jr. et al. These patents are incorporated herein by reference.

While applicant does not wish to be bound by any particular theory or mechanism as to the precise manner in which the softeners function to improve the feel or hand of laundered textiles, it is believed that the phosphinate compound attaches to the laundered textile material at the acid, salt or ester portion of the molecule. The one or two pendant long chain alkyl groups are believed to exert a lubricity effect on the fibers of the laundered textile thereby improving the feel or hand. This belief is substantiated at least in part by the observation that alkylphosphonate compounds belonging to the class of compounds having the formula II/ P Ahereinbefore described.

These compounds are characterized by the presence of a P- C-P linkage in their molecules and are generically termed methylene diphosphonic acids, salts of methylene diphosphonic acids and alkyl esters of methylene diphosphonic acids. As employed hereinafter the general term methylene diphosphonate is intended as embracing the acid, salt and ester forms.

The methylene diphosphonates of the present invention are characterized by the presence of a long-chain alkyl group of about 12 to about 30 carbon atoms. These compounds, like the phosphinate compounds described hereinbefore, are believed to function according to the mechanism whereby the methylene diphosphonate compound attaches to laundered textile material, the pendant alkyl group serving to provide lubricity to the textile fibers thereby imparting improved feel or hand to the laundered fabric.

The methylene diphosphonate compounds of the present invention can be employed to advantage as fabric softeners in either their acid, salt or ester forms as hereinbefore stated. Thus, each M is selected from hydrogen, alkali metal (e.g., sodium, potassium, lithium), ammonium, substituted ammonium, or alkyl of about one to about eight carbon atoms.

Preferred methylene diphosphonate compounds of the present invention are the acid and alkali metal salt forms of methylene diphosphonic acids having a pendant alkyl of about 16 to about 24 carbon atoms, these being preferred from the standpoints of excellent softening properties, remarkable compatibility with anionic surfactants and ease of preparation. Examples of methylene diphosphonate compounds include the following which are intended as being illustrative rather than limitative: tridecylidene diphosphonic acid; tetradecy- .19.. in the embodiment of this invention which provides for a built liquid detergent, a hydrotropic agent may at times be found desirable. Suitable hydrotropes are water-soluble alkali lidene diphosphonic acid; pentadccyiidene diphosphonic acid;

hexadecylidene diphosphonic acid; heptadecylidene diphosphonic acid; octadecylidene diphosphonic acid; nonadecylidene diphosphonic acid; eicosyiidene diphosphonic acid; heneicosylidene diphosphonic acid; docosylidene diphosphonic acid; tricosylidene diphosphonic acid; tetracosylidene diphosphonic acid; pentacosylidene diphosphonic acid; hexacosylidene diphosphonic acid; heptacosylidene diphosphonic acid; octacosylidene diphosphonic:

acid; nonacosylidene diphosphonic acid; triacontylidene- 2 diphosphonic acid; hentriacontylidene diphosphonic acid; itrisodium tridecylidene diphosphonate; tetrasodium pen- 'tadecylidene diphosphonate; tetrapotassium heptadecylidene diphosphonate; tetraammonium nonadecylidene E diphosphonate; tripotassium heneicosylidene diphosphonate; disodium dicosylidene diphosphonate; dipotassium pentacosylidene diphosphonate; diammonium hentriacontylidenei diphosphonate; tetramethyl heptadecylidene diphosphonaten tetrabutyl nonadecylidene diphosphonate; tetrahexylhencosylidene diphosphonate; tetraoctyl tricosylidne diphosphonate.

The class of methylene disphosphonate compounds of the present invention are known compounds and can be prepared. by methods known to those skilled in the art. The methylene diphosphonate esters hereinbefore described can be conveniently prepared by preparing a metallo-derivative of a methylene diphosphonate ester and reacting this metalloderivative with an organo-halide to produce the desired methylene diphosphonate ester. Methylene disphosphonic acid compounds can be conveniently prepared by hydrolysis of the corresponding ester compounds with a concentratedv mineral acid (e.g. NaOl-i) while the salts of methylene diphosphonic acid can be readily prepared by neutralizing the acid compound with an appropriate basic compound (e.g. NaOl-i). Methods of preparing methylene diphosphonate compounds are described in U.S. Pat. No. 3,299,123 issued Jan. 17, l967 to Fitch et al. This reference is hereby incorporated by reference.

The detergent softener compositions of the present invention can be formulated into any of the several commercially; desirable composition forms, for example, granular, flakefl liquid and tablet forms. in a finished formulation of this inven-? tion there will often be added in minor amounts materials which make the product more effective or more attractive, The following are mentioned by way of example. A soluble sodium carboxymethyicellulose can be added in minor amounts to inhibit soil redeposition. A tarnish inhibitor such as benzotriazole or ethylenethiourea may also be added in amounts up to about 2 percent. Fluorescers, perfume and color while not essential in the compositions of the invention, can be added in amounts up to about 1 percent. An alkaline material or alkali such as sodium hydroxide or potassium hydroxide can be added in minor amounts as supplementary pH adjusters. There might also be mentioned as suitable additives moisture. brightening agents. sodium sulfate. fatty acid soaps, enzymes and sodium carbonate.

Corrosion inhibitors generally also added. Soluble silicates are highly effective inhibitors and can be added to certain formuias of this invention at levels of from about 3 percent to? about 8 percent. Alkali metal, preferably potassium or sodium, silicates having a weight ratio of SiO,M,O of from 1.021 to 2.8:] will be used. M in this ratio refers to sodium and potassijum. A sodium silicate having a ratio of SiO,:Na,O of about 1.6:l to 2.45:] is especially preferred for economy and effectiveness.

metal salts of to luenesu lfonate, benzenesulfonate, and xylenesulfonate. The preferred hydrotropes are the potassium or sodium toluenesulfonates. The hydrotrope salt may be added, if desired, at levels of 0 percent to about 12 percent. While a hydrotrope will not ordinarily be found necessary, it can be added if so desired for any reason such as to produce a product which retains its homogeneity at a low temperature.

The detergent softener compositions of the present invention can be employed to advantage in home and commercial laundry situations to provide conjoint washing and softening effects. These compositions impart excellent softening effects to all types of textile materials including cottons, wooiens, silks and synthetics such as nylon, dacron, creslan or the like. The advantageous conjoint washing and softening effects described herein are not limited to any essential temperature 0 conditions; they can be achieved, for instance, by conducting the washing process at temperatures of about 40 F. to about 180 F. Cool water washing as used herein contemplates washing at temperatures below the very hot water washing com- .monly encountered in general household laundering situations and contemplates washing at about 40 F. to about l00 F. Normally, the conjoint washing and softening effects can be obtained by conducting the laundering process in an aqueous solution of a detergent softener composition described hereinbefore and is conducted in the presence of at least about 16 ppm. of the organic phosphorus-containing softener compound of the present invention. When so treated, most textile materials are characterized by excellent hand or feel. ;Preferabiy, a washing solution having about 32 to about 1 i2 p.p.m. of the organic phosphorus-containing softener compound is employed for superior softening effects and economy.

The following exampies are presented to illustrate the invention, with parts by weight being used in the examples unisss t sa q- W EXAMPLE I A granular detergent composition was prepared by mixing the individual ingredients in a crutcher in a conventional ingredients manner with sufficient water to form a detergent slurry. The slurry was oven dried to remove excess moisture and to form detergent granules.

Parts by Weight Sodium straight chain alkyl benzene sulfonate having an average chain length of about 5 ll.8 carbon atoms |5.0 isodium tripolyphosphste 50.0 Sodium silicate having an SiO, Na, 0 ratio of L6: l 6.0

Sodium carbosymethylcelluiose 0.3 Sodium sulfate l5.7

Dim-eicosylphosphinic acid 3.0

Water I01) tadecylphosphinic acid; n-nonadecylphosphinic acid; eicosylphosphinic acid; n-heneicosylphosphinic acid; docosylphosphinic acid; n-tricosylphosphinic acid; tetracosylphosphinic acid; n-pentacosylphosphinic acid; hexacosylphosphinic acid; n-heptacosylphosphinic acid; n-octacosylphosphinic acid; n-nonacosylphosphinic acid; ntriacontylphosphinic acid; sodium n-dodecylphosphinate; potassium n-tetradecylphosphinate; lithium n-hexadecylphosphinate; sodium octadecylphosphinate; potassium neicosylphosphinate; sodium n-docosylphosphinate; potassium n-tetracosylphosphinate; sodium n-hexacosylphosphinate; lithium n-octacosylphosphinate; lithium n-triacontylphosphinate; methyl n-dodecylphosphinate; ethyl n-tetradecylphosphinate; isopropyl n-tetradecylphosphinate; Z-ethylhexyl nhexadecylphosphinate; methyl n-eicosylphosphinate; ethyl ntetracosylphosphinate; butyl n-octacosylphosphinate; butyl ntriacontylphosphinate; ammonium n-hexadecylphosphinate; ammonium n-octadecylphosphinate; dimethylammonium neicosylphosphinate, trimethylammonium n-eicosylphosphinate; ammonium n-tetraoosylphosphinate; n-dodecylmethylphosphinic acid; n-tridecylmethylphosphinic acid; ethyl-n-tetradecylphosphinic acid; ethyl-n-hexadecylphosphinic acid; methyl-n-octadecylphosphinic acid; n-eicosylmethylphosphinic acid; n-do-cosylhexylphosphinic acid; di-ndodecylphosphinic acid; di-n-hexadecylphosphinic acid; di-noctadecylphosphinic acid; sodium methyl-n-octacosylphosphinate; potassium di-n-dodecylphosphinate; sodium di-ntetradecylphosphinate; potassium di-n-hexadecylphosphinate; lithium di-n-octadecylphosphinate; ammonium di-neicosylphosphinate; sodium di-n-eicosylphosphinate; trimethylammonium di-n-docosylphosphinate; sodium di-nhexacosylphosphinate, sodium di-n-octacosylphosphinate; and sodium di-n-triacontylphosphinate; methyl di-neicosylphosphinate; 2-ethylhexyl di-n-eicosylphosphinate; and the isomers thereof.

EXAMPLE 11 A granular detergent composition was prepared according to the procedure of example I except that five parts of the din-eicosylphosphinic acid were employed. The two additional parts of softener compound replaced two parts of the sodium sulfate.

This composition imparts excellent softness to laundered textiles when employed in a laundering solution containing about 240 p.p.m. It is an effective cleaning composition.

EXAMPLES lll AND lV Granular detergent compositions were prepared according to the procedures of examples I and ll, respectively, except that in each instance the phosphinate employed was a mixture of dialkylphosphinic acid compounds having a random distribution of alkyl groups ranging from 14 to 22 carbon atoms, prepared by reaction at 80 C. of 2 moles of a mixture of aolefms with one mole of hypophosphorous acid. The distribution of a-olefins employed in the reaction with hypophosphorous acid was as follows:

C 3.8 percent (by weight) (2,, I23 percent u 33.9 percent C- I 37.6 percent C" l L8 percent These compositions combine advantageous softening and cleaning effects in the laundering of most textile materials.

When the following builder salts are employed in place of sodium tripolyphosphate, substantially similar results are obtained in that effective cleaning and softening formulations are employed: sodium tetraborate; potassium bicarbonate; sodium carbonate; sodium pyrophosphate; sodium orthophosphate, potassium hexametaphosphate; sodium ethylenediaminetetraacetate, potassium nitrilotriacetate; sodium N-( 2-hydroxyethyl)nitrilo diacetate; sodium phytate; sodium, potassium and lithium salts of ethane-l-hydroxy-l,ldiphosphonic acid; sodium, potassium and lithium salts of ethylene diphosphonic acid; sodium, potassium and lithium salts of l,l,2-triphosphonic acid; sodium, potassium and lithium salts of ethane-Z-carboxy-l ,l-disphosphonic acid, hydroxymethanediphosphonic acid, carbonyldiphosphonic acid, ethane-l-hydroxy-l ,l,2triphosphonic acid, ethane-Z-hydroxyl l ,2,-triphosphonic acid, 3, propanel l ,3,3- tetraphosphonic acid, propane-Ll,2,3-tetraphosphonic acid, and salts of polymers of itaconic acid, aconitic acid, maleic acid, mesaconic acid, furnaric acid, methylene malonic acid and citraconic acid and copolymers with themselves and/or ethylene and/or acrylic acid in, e.g.,l :1 molar ratios and having molecular weights of 75,000; l00,000; and l25,000 (the copolymers with ethylene and/or acrylic acid having equivalent weights, based on the acid form of 65, 70 and 75); in the form of their sodium, potassium, triethanolammonium, diethanolammonium and monoethanolarnmonium salts.

EXAMPLE V A granular detergent composition having the following composition was prepared according to the procedure of example 1:

Parts by Weight Sodium straight chain alkyl benzene sulfonale having an average chain length of about I 1.8 carbon atoms 20 Sodium tripolyphosphate 50 Sodium silicate having a sit), :Na, 0 ratio of 1.6 l 6 Sodium carboxyrnethylcellulose 0.3 Sodium sulfate l0.7 Hcptadecylidene diphosphonic acid C H a CH PO (OH I 3.0 Water 10.0

This composition combines cleaning and softening properties in the same formulation.

Substantially similar results are obtained when the following softener compounds are employed in lieu of heptadecylidene diphosphonic acid: tridecylidene diphosphonic acid; tetradecylidene diphosphonic acid; pentadecylidene diphosphonic acid; hexadecylidene diphosphonic acid; octadecylidene diphosphonic acid; nonadecylidene diphosphonic acid; eicosylidene diphosphonic acid; heneicosylidene diphosphonic acid; docosylidene diphosphonic acid; tricosylidene diphosphonic acid; tetracosylidene diphosphonic acid; pentacosylidene diphosphonic acid; hexacosylidene diphosphonic acid; heptacosylidene diphosphonic acid; octacosylidene diphosphonic acid; nonacosylidene diphosphonic acid; triacontylidene diphosphonic acid; hentriacontylidene diphosphonic acid; trisodium tridecylidene diphosphonate; tetrasodium pentadecylidene diphosphonate; tetrapotassium heptadecylidene diphosphonate; tetraammonium nonadecylidene diphosphonate; tripotassium heneicosylidene diphosphonate; disodium discosylidene diphosphonate; dipotassium diphosphonate; diammonium hentriacontylidene diphosphonate; tetramethyl heptadecylidene diphosphonate; tetrabutyl nonadecylidene diphosphonate; tetrahexyl hencosylidene diphosphonate; tctraoctyl tricosylidcne diphosphonate.

EXAMPLE VI An excellent built liquid detergent formation according to this invention which combines superior cleaning and softening properties has the following composition, in which amounts are expressed in percentage by weight.

Sodium dedcylbensenesulfonate (the dodecyl radical being a popypmpylene, predominantly ten-propylene averaging l2 carbon atoms) 60 Dimethyldodecylamine oxide 6.0%

'l'r'nodium ethane-Lhydroxyl. l -dipho|phonnte 20.0% Potassium tolueneaulfonate 8.0% Sodium silicate (ratio SiO,:Na,O of 2.45:1) 3.8% Carboxymethyl hydroxyethyl cellulose 0.3% Sodium-n-eicosylmethylphosphinate 5.0% Water Balance Substantially similar results are obtained when the following softener compounds are employed in lieu of sodium eicosylmethylphosphinate in that a product exhibiting both cleaning and softening properties is obtained: sodium dodecylmethylphosphinate; sodium-n-tetradecylmethylphosphinate; potassium n-hexadecylmethylphosphinate; potassium-n-octadecyl-n-propylphosphinate; lithium-n-eicosylmethylphosphinate; lithium-n-docosylmethylphosphinate; ammonium methyl-n-tetracosylphosphinate; trimethylammonium methyln-triacontylphosphinate.

in the the above example the following organic detergents are substituted, either wholly or in part (e.g., a lzl ratio) for the said sodium alkyl benzene sulfonate having an average chain length of about 12 carbon atoms, substantially equivalent results are obtained in that the detergent composition is an effective cleaning and softening formulation:

1. The following anionic synthetic detergents wherein the cations are sodium, potassium, ammonium, monoethanolammonium, diethanolammonium, triethanolammonium cations. Alkyl sulfates wherein the alkyl group is derived from tallow or coconut oil; alkyl benzene sulfonates in which the alkyl groups contain nine, ll, l2, 13 or 15 carbon atoms; alkyl glycidyl ether sulfonates derived from tallow or coconut oils; coconut fatty acid monoglyceride sulfates and sulfonates; salts of sulfuric esters of the reaction product of 1 mole of tallow or coconut oil fatty alcohols and 3 or 4 moles of ethylene oxide; alkyl phenol ethylene oxide ether sulfates containing four or nine ethylene oxide moieties per molecule and in which the alkyl radical contains nine, l2, 13 or 15 carbon atoms; the neutralized reaction product of coconut fatty acids with isethionic acid; coconut fatty acid amide of methyl taurine salts;

2. The following nonionic detergents: the condensation product of propylene oxide with propylene glycol, the ethylene oxide portion of the compound being 50 percent of the total weight of the compound and the total molecular weight of the compound being about 1,700; the condensation product of alkyl phenols containing nine or 12 carbon atoms in the alkyl group with l0, 15 or 20 moles of ethylene oxide per mole of alkyl phenol; the condensation product of ethylene oxide with the condensation product of propylene oxide and ethylene diamine wherein the product contains about 65 percent polyethylene oxide by weight and the total molecular weight of the compound is about 6,000; the condensation product of coconut oil fatty alcohol and about 15 moles of ethylene oxide per mole of coconut alcohol;

3. The following semipolar detergents:

dimethyldodecyl amine oxide,

oleyldi (2 hydroxyethyl) amine oxide,

dimethyloctylamine oxide,

dimethyldecylamine oxide,

dimethyltetradecylamine oxide,

3,6,9 trioxaheptadecyldiethylamine oxide,

di(2-hydroxyethyl) tetradecylamine oxide,

2-dodecoxyethyl dimethylamine oxide,

3-dodecoxy-2-hydroxy propyl di(3-hydroxypropyl)-amine 6 oxide, dimethylhexadecylamine oxide, dodecyldimethylphosphine oxide, tetradecyldimethylphosphine oxide, tetradecylmethylethylphosphine oxide, 3,6,9-trioxaoctadecyldimethylphosphine oxide, cetyldimethylphosphine oxide, 3-dodecoxy-2-hydroxypropyldi( 2-hydroxyethyl)phosphine oxide, stearyldimethylphosphine oxide, cetylethylpropylphosphine oxide,

14 oleyl diethylphosphine oxide, dodecyldiethylphosphine oxide, tetradecyldiethylphosphine oxide, dodecyldipropylphosphine oxide, dodecyldi (hydroxymethyl) phosphine oxide, dodecyldi (Z-hydroxyethyl) phosphine oxide, tetradecylmethyl-Z-hydroxypropyl phosphine oxide, oleyldirnethylphosphine oxide, Z-hydroxydodecyldimethylphosphine oxide, octadecyl methyl sulfoxide, 3,6,9-trioxaoctadecyl Z-hydroxyethyl sulfoxide, dodecyl methyl sulfoxide, oleyl S-hydroxy propyl sulfoxide, tetradecyl methyl sulfoxide, 3-methoxytridecyl methyl sulfoxide, 3-hydroxytridecyl methyl sulfoxide, 3-hydroxy-4-dodecoxybutyl methyl sulfoxide, 4. The following ampholytic detergents: sodium 3- 0 dodecylaminopropionate, sodium 3-dodecylaminopropane-l- EXAMPLE Vll An excellent granular detergent composition providing outstanding cleaning and softening in washing situations has the following ingredients in the percentages indicated:

Sodium dodecylbenzenesulfonate (dodecylgroup derived from tetrapropylene l7 5' Potassium toluenesulfonate 2.0% Sodium tripolyphosphate 45.0!

Sodium silicate (ratio Si0,:Na,0 of2zl) tm 6.0%

Sodium sulfate l 1.8% Coconut fatty acid ethanolamide 2.7'i Ammonium ethyl-n-tetracosylphotphinate 4.0! Moisture Balance Substantially similar results are obtained when the following organic detergents are employed in place of sodium dodecylbenzenesulfonate in that effective cleaning and softening formulations are obtained: sodium decylbenzene sulfonate; sodium tridecylbenzene sulfonate, sodium hexadecylbenzene sulfonate, sodium octadecylbenzene sulfonate, sodium octadecyl sulfate sodium hexadecyl sulfate, sodium tetradecyl sulfate, and sodium dodecyl sulfate, sodium tetradecene sulfonate, sodium dodecyl glyceryl ether sulfonate, sodium salts of the sulfated reaction product of 1 mole of coconut fatty alcohol 5 and 3 moles of ethylene oxide.

EXAMPLE Vlll A granular detergent composition providing excellent cleaning and softening properties has the following formula- 70 tion:

Sodium alkylbenzenesulfonate (the alkyl group being a mixture of C,"C,. and C carbon atoms.

averaging C 7.59 Nonionic active (a mixture of performances.

1.5% Ucon and 0.5% Pluronic L-64) 2.0% Hydrogenated marine oil fatty acid 2.2% Sodium tripolyphoaphate 47.6% Sodium nitrllotriacetate 1.0% Sodiium silicate (ratio SiO,:Na,0 of 2:1) 9.7% Sodium rulfate H.596 Z-ethylhexyl ester of n-tetracoaylphoaphinic acid 4.0% Water Balance l Condensation products of ethylene oxide with a hydrophobic base formed by the condensation of propylene oxide with propylene glycol and having molecular weights of approximately characteristics of this composition are exceptionally good from the point of view of general cleaning and whiteness maintenance EXAMPLE IX An effective cool water built liquid detergent which performs exceptionally well as a heavy-duty detergent composition, especially in the areas of cleaning and softening, has the following composition:

3(N.N-dimethyl-N-hexadecylammonio)' Z-hydrozypropanel-aulfonate l 1.0% Sodium pyrophoaphate 18.0% Sodium silicate (SiO,:Na,lI 1.621) 3.8% Potassium toluenesulfonate 8.5% Sodium carboxymethyl hydroxyethyl cellulose 0.3%

Fluorescent dye .l2% Perfume .15% Benzolriazole 0.02% Tetraethyl tridecylidenc diphosphonate (C,,l'l ClllP()(C,H,),h 4.0% Water 54.] I;

Substantially similar results are obtained when the following softener compounds are employed in place of tetraethyl tridecylidene diphosphonate in that formulations combining effective cleaning and softening properties are obtained: tetramethyl heptadecylidene diphosphonate; tetrabutyl octadecylidene diphosphonate; tetrapropyl nondecylidene, diphosphonate; tetrabutyl eicosylidene diphosphonate; tetramethyl hencosylidene diphosphonate; tetraoctyl triacosylidene diphosphonate; tetramethyl pentacosylidene diphosphonate.

EXAMPLE X An effective built granular composition providing superior cleaning and softening has the following compositions:

Sodium hexadecyl sulfate "0% Sodium tripolyphosphate 43.0% Sodium silicate (Na,0:5i0\, I l:2.5) 6.0% Sodium carbozymethyl cellulose 0.3% Sodium sulfate 26. 5 Sodium di-n-octadecylphosphinate 4.0% Water 3.5% Miscellaneous Balance cleaning and softening effects to laundered fabrics has the following composition:

Sodium hexadecyl sulfate Di-n-eicosylphosphinic acid All or a portion of the di-n-eicosylphosphinic acid can be replaced with eicosylidene diphosphonic acid with substantially similar results.

The excellent softening properties of detergent compositions of the present invention were evaluated according to the following procedure. Three 15 inches X 15 inches cotton terrycloth swatches were laundered with a washing solution of the test composition in water of 7-grain hardness and 120 F. temperature using a miniature l-gallon washing machine equipped with a mechanical agitator. The detergent softener composition identified below in table I as examples l-V were those specifically described and listed above under the corresponding example numbers. The test products were employed in amounts sufficient to provide the concentration of softener compound in washing solution shown in table I. Following a [0-minute washing cycle and two rinse cycles, the fabrics were dried. This procedure, representing one cycle, was repeated for a total of six cycles for each test composition. A panel pf five experts evaluated the dried swatches for softness after the second, fourth and sixth cycles, comparing the softness of the treated swatches with the feel of swatches treated with a washing solution containing 6 guts. of a control composition corresponding to that of example I but having no phosphinic acid softener compound present. The results tabulated below in table 1 indicate the percentage of expert graders preferring the softness and feel of terrycloths treated with compositions of the present invention as compared to those treated in the same manner with the control composition.

TABLE 1 Cycle Concentration of Softener Compound Formulation p.p.|n. 2 4 6 Example I 40! 48 BOK 80! Example I! so 100% most so; Example ill 48 I00; l00'ii 1001 Example IV 80 I00; 100% I00; Example V 48 80% I00; 80!

wherein R and R are eaghf'alkyl of about l6 to about 24 carbon atoms and M is a w'tfrssolubilizing cation selected from the group consisting ofifhydrogen, alkali metal cations, am-

monium, methylammonium, dimethylammonium, trimethylammonium, tetramethylammonium, dimethylpiperdinium and alkyl of l to about 8 carbon atoms.

2. The detergent composition of claim 1 wherein there is present a water-soluble builder salt in a ratio of water-soluble builder salt to synthetic organic nonsoap detergent of about 30:1 to about 0.25:1.

3. The detergent composition of claim 2 wherein M is hydrogen.

4. The detergent composition of claim 3 wherein the dialkylphosphinic compound is present in an amount of about 2 to about 7 percent and the synthetic organic nonsoap detergent is an anionic detergent.

5. The detergent composition of claim 4 wherein the synthetic organic nonsoap detergent is an alkali metal alkylbenzene sulfonate having an alkyl group of about nine to about 18 carbon atoms.

6. The detergent composition of claim 5 wherein the watersoluble builder is sodium tripolyphosphate and is present in a ratio of sodium tripolyphosphate to alkali metal alkylbenzene sulfonate of about 9:1 to about 0.5:1.

7. The detergent composition of claim 2 wherein M is alkali metal.

8. The composition of claim 7 wherein the dialkylphosphinic compound is present in an amount of about 2 to about 7 percent and the synthetic nonsoap detergent is an anionic detergent.

9. The detergent composition of claim 8 wherein the synthetic organic nonsoap detergent is an alkali metal alkylbenzene sulfonate having an alkyl group of about nine to about 18 carbon atoms.

10. The detergent composition of claim 9 wherein the water-soluble builder is sodium tripolyphosphate and is present in a ratio of sodium tripolyphosphate to alkali metal alkylbenzene sulfonate of about 9: l to about 0.5: l

11. The process of conjointly washing and softening textile materials which comprises washing said textile materials at a temperature of about 40 to about F. with an aqueous solution of a detergent composition of claim 1, said aqueous solution having at least about 16 ppm. of the organic phosphorous-containing softener compound.

roqoso Patent No.

Inventor-(s) CERTI Melvin FICATE OF CORRECTION O75 a d September 28, 1971 A. Barbera It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

r- Column 3, line 2, waterhsoluble" should be watersoluble Column 4, line 53, "3,528,378" should be 2,528,378 Column 5, line 20, "3 Examples" should be Examples Column 5, line 69, delete "3) and insert and therefor.

Column 6, line 5, "ethene" should be ethane Column 6, line 8 (3) should be (4) Column 7, line 22, after "eight" insert carbon Column 8, line 51, "Ahereinbefore" should be hereinbefore Column 9, line 67, after the word "generally" insert are Column 11, line 55, "80C" should be 85C Column 12, line 12, after "acid," delete 3, Column 12, line 60, after "dipotassium" insert pentacosylidene Column 12, line 73, "popypropylene" should be polypropylene Column 13, line 19, before "in" insert When Column 14, line 20, "dodecye" should be dodecyl Column 14, line 28, "hydroxyporplammonio" should be hydroxypropylammonio Column 14, line 33, "butone" should be butane Column 14, line 51, delete "tm" Column 15, line 57, "carbozymethyl" should be carboxymethyl Column 16, line 46, "40%" should be under column "2" Signed and sealed this 6th day of June 1972.

(SEAL) Attest:

EDWARD M.FLETCHER, JR.

Attesting Officer ROBERT GOITSGILQLK Commissioner of Patents 

2. The detergent composition of claim 1 wherein there is present a water-soluble builder salt in a ratio of water-soluble builder salt to synthetic organic nonsoap detergent of about 30:1 to about 0.25:1.
 3. The detergent composition of claim 2 wherein M is hydrogen.
 4. The detergent composition of claim 3 wherein the dialkylphosphinic compound is present in an amount of about 2 to about 7 percent and the synthetic organic nonsoap detergent is an anionic detergent.
 5. The detergent composition of claim 4 wherein the synthetic organic nonsoap detergent is an alkali metal alkylbenzene sulfonate having an alkyl group of about nine to about 18 carbon atoms.
 6. The detergent composition of claim 5 wherein the water-soluble builder is sodium tripolyphosphate and is present in a ratio of sodium tripolyphosphate to alkali metal alkylbenzene sulfonate of about 9:1 to about 0.5:1.
 7. The detergent composition of claim 2 wherein M is alkali metal.
 8. The composition of claim 7 wherein the dialkylphosphinic compound is present in an amount of about 2 to about 7 percent and the synthetic nonsoap detergent is an anionic detergent.
 9. The detergent composition of claim 8 wherein the synthetic organic nonsoap detergent is an alkali metal alkylbenzene sulfonate having an alkyl group of about nine to about 18 carbon atoms.
 10. The detergent composition of claim 9 wherein the water-soluble builder is sodium tripolyphosphate and is present in a ratio of sodium tripolyphosphate to alkali metal alkylbenzene sulfonate of about 9:1 to about 0.5:1.
 11. The process of conjointly washing and softening textile materials which comprises washing said textile materials at a temperature of about 40* to about 180* F. with an aqueous solution of a detergent composition of claim 1, said aqueous solution having at least about 16 p.p.m. of the organic phosphorous-containing softener compound. 